The present invention relates to novel manganese complexes of salen ligands and to the use thereof as catalysts that enhance the action of peroxy compounds in washing, cleaning and disinfecting processes. The invention furthermore relates to formulations used in such processes that comprise the manganese complexes and peroxy compounds, and also to the novel ligands and to processes for the preparation thereof.
A number of manganese complexes of the salen type are already known to be suitable catalysts for oxidations that use peroxy compounds, especially within the context of washing procedures. Also, certain other manganese complexes have already been described as having a pronounced bleaching action on dirt and dyes in washing liquors. There is nevertheless still a need for further compounds having improved action and/or a broader field of application, but such compounds should not cause any appreciable damage to fibres or colours when used on textile material.
It has now been found that certain novel manganese complexes of the salen type as catalysts largely meet the required conditions. They enhance the action of peroxy compounds in a very wide variety of applications, substantially without damage occurring to fibres or colours. Surprisingly, when the manganese complexes according to the invention are employed in aqueous solution together with peroxy compounds, the enhanceed action occurs in the following applications:
a) the bleaching of stains or soiled areas on textile material within the context of a washing procedure,
b) the inhibition of migrating dyes being redeposited when textile material is washed,
c) the cleaning of hard surfaces, especially crockery or glass,
d) the cleaning of hard surfaces, especially glazed tiles or floor tiles, especially for the removal of stains that have formed as a result of the action of molds (mold stains), and
e) the use of washing and cleaning solutions that have an antibacterial activity.
The present invention accordingly relates to compounds of formula 
wherein
n is 0, 1 or 2,
m is 1 or 2,
A is an anion;
Y is a linear or branched alkylene radical of formula xe2x80x94[C(R5)2]rxe2x80x94 wherein r is an integer of from 1 to 8 and the R5 radicals are each independently of the others hydrogen or C1-C4alkyl; xe2x80x94CXxe2x95x90CXxe2x80x94 wherein X is cyano, linear or branched C1-C8alkyl or di(linear or branched C1-C8alkyl)amino; xe2x80x94(CH2)qxe2x80x94NR4xe2x80x94(CH2)qxe2x80x94 wherein R4 is hydrogen or C1-C4alkyl and q is 1, 2, 3or 4; or
a 1,2-cyclohexylene radical of formula: 
xe2x80x83or a 1,2-aryl radical of formula 
xe2x80x83wherein R9 is hydrogen, SO3H, CH2OH or CH2NH2,
R and R1 are each independently of the other nitro, NR6R7 wherein R6 is hydrogen or linear or branched C1-C12alkyl and R7 is linear or branched C1-C12alkyl, with the proviso that R6 and R7 in the groups NR6R7 are not identical, or xe2x80x94CH2xe2x80x94N⊕R4R6R7 or xe2x80x94N⊕R4R6R7 wherein R4, R6 and R7 are as defined above,
R2 and R3 are each independently of the other hydrogen, linear or branched C1-C4alkyl, unsubstituted aryl, or aryl substituted by cyano; by halogen; by OR5 or COOR5 wherein R5 is hydrogen or linear or branched C1-C4alkyl; by nitro; by linear or branched C1-C8alkyl; by NHR6 or NR6R7 wherein R6 and R7 are identical or different and are each linear or branched C1-C12alkyl; by linear or branched C1-C8alkyl-R8 wherein R8 is a radical OR5, COOR5 or NR6R7 as defined above or is NH2; or by xe2x80x94N⊕R4R6R7 wherein R4, R6 and R7 are as defined above,
and, when n and m are each 1, R2 and R3 are each hydrogen and Y is unsubstituted 1,2-cyclohexylene, R and R1 are not each nitro in the 5- and 5xe2x80x2-position, respectively, and, when n and m are each 1, R2 and R3 are each hydrogen and Y is unsubstituted 1,2-ethylene, R and R1 are not each N⊕(CH3)(C2H5)2 in the 4- and 4xe2x80x2-position, respectively.
In compounds of formula (1) in which n is 2, the radicals R may have identical or different meanings. The same applies to compounds of formula (1) in which m is 2 in respect of the radicals R1.
When Y is a 1,2-cyclohexylene radical, that radical may be in either of its stereoisomeric cis/trans forms.
Preferably, Y is a cyclohexylene radical, a radical of formula (CH2)rxe2x80x94 wherein r is an integer of from 1 to 8, or a radical of formula xe2x80x94C(R5)2xe2x80x94(CH2)pxe2x80x94C(R5)2xe2x80x94 wherein p is an integer of from 0 to 6 and R5 is hydrogen or C1-C4alkyl.
In especially preferred compounds of formula (1), Y is a cyclohexylene radical, a radical of formula xe2x80x94(CH2)rxe2x80x94 wherein r is an integer of from 1 to 4, or a radical of formula xe2x80x94(CR5)2xe2x80x94(CR5)2xe2x80x94 wherein the R5 radicals are each independently of the others hydrogen or methyl.
Halogen is preferably chlorine, bromine or fluorine, chlorine being especially preferred.
When n or m is 1, the groups R and R1 are preferably in the 4- or 5-position of the respective benzene ring.
When R6 or R7 is an alkyl radical, the alkyl group may be straight-chain or branched. Preferably, the alkyl group contains from 1 to 8, especially from 1 to 4, and more especially from 1 to 3, carbon atoms.
Preferably, the radicals R and R1 are each nitro, NR6R7 wherein R6 and R7 are each C1-C4alkyl, with the proviso that R6 and R7 are not identical, or xe2x80x94N⊕R4R6R7 wherein R4, R6 and R7 are each C1-C4alkyl.
The radicals R2 and R3 are especially hydrogen, methyl, ethyl, or unsubstituted phenyl.
Aryl is, for example, naphthyl or, especially, phenyl.
Suitable anions include, for example, halide, for example chloride, bromide or iodide, perchlorate, sulfate, nitrate, hydroxide, BF4xe2x88x92, PF6xe2x88x92, carboxylate, acetate, tosylate and triflate. Of those, preference is given to chloride, bromide, iodide and acetate.
The compounds of formula (1) are prepared, for example, in a manner known per se from the corresponding ligands and a manganese compound. Preparation processes of that kind are described, for example, in U.S. Pat. Nos. 5,281,578 and 4,066,459.
The ligands of formula 
wherein R, R1, R2, R3, Y, n and m are as defined for formula (1) are likewise novel. They are prepared in a manner known per se, for example by reacting a diamine of formula H2Nxe2x80x94Yxe2x80x94NH2 first of all with an aldehyde or ketone of formula 
and then with an aldehyde or ketone of formula 
In formulae (3) and (4), R, R1, R2, R3, n and m are as defined for formula (1). When, in the compounds of formula (2), (R)n has the same meaning as (R1)m and R2 has the same meaning as R3 then, for the synthesis of compounds of formula (2), one mol of a diamine of formula H2Nxe2x80x94Yxe2x80x94NH2 is reacted with two mols of an aldehyde or ketone of formula (3).
The diamines of formula H2Nxe2x80x94Yxe2x80x94NH2 and the aldehydes or ketones of formula (3) and (4) are known or can be prepared in a manner known per se.
The compounds of formula (1) are used as catalysts for oxidations using peroxy compounds, for example for bleaching textile material, without causing appreciable damage to fibres and colours.
The present invention accordingly further relates to a washing and cleaning process which comprises adding to the liquor, which comprises a peroxide-containing washing and cleaning agent, from 0.1 to 200 xcexcmol of one or more compounds of formula (1) per liter of washing liquor.
The present invention relates also to a method of inhibiting the redeposition of migrating dyes present in a washing liquor, which comprises adding to the washing liquor, which comprises a peroxide-containing washing agent, from 0.5 to 150 mg, preferably from 1.5 to 75 mg, especially from 7.5 to 40 mg, of one or more compounds of formula (1) per liter of washing liquor.
The present invention relates furthermore to a washing agent containing
I) from 5 to 90%, preferably from 5 to 70%, A) of an anionic surfactant and/or B) of a non-ionic surfactant,
II) from 5 to 70%, preferably from 5 to 50%, especially from 5 to 40%, C) of a builder substance,
III) from 0.1 to 30%, preferably from 1 to 12%, D) of a peroxide and
IV) from 0.005 to 2%, preferably from 0.02 to 1%, especially from 0.1 to 0.5%, E) of a compound of the above-defined formula (1), the percentages in each case being percentages by weight, based on the total weight of the washing agent.
The washing agent may be in solid or liquid form, for example in the form of a liquid, non-aqueous washing agent containing not more that 5%, preferably from 0 to 1%, by weight of water, and may comprise as base a suspension of a builder substance in a non-ionic surfactant, for example as described in GB-A-2 158 454.
The washing agent is preferably, however, in the form of a powder or granules.
The powder or granules can be prepared, for example, by first preparing a starting powder by spray-drying an aqueous suspension comprising all of the above-listed components with the exception of components D) and E), and then adding the dry components D) and E) and mixing everything together.
It is also possible to add component E) to an aqueous suspension comprising components A), B) and C), then subject the mixture to spray-drying and subsequently mix component D) with the dry mass.
It is furthermore possible to start with an aqueous suspension that comprises components A) and C) but not component B) or only a proportion of component B). The suspension is spray-dried and then component E) is mixed with component B) and added, and subsequently component D) is admixed dry.
The anionic surfactant A) may be, for example, a sulfate, sulfonate or carboxylate surfactant or a mixture of such surfactants.
Preferred sulfates are those having from 12 to 22 carbon atoms in the alkyl radical, if desired in combination with alkylethoxysulfates in which the alkyl radical contains from 10 to 20 carbon atoms.
Preferred sulfonates include, for example, alkylbenzenesulfonates having from 9 to 15 carbon atoms in the alkyl radical.
The cation in the anionic surfactants is preferably an alkali metal cation, especially sodium.
Preferred carboxylates are alkali metal sarcosinates of formula Rxe2x80x94COxe2x80x94N(R1)xe2x80x94CH2COOM1, wherein R is alkyl or alkenyl having from 8 to 18 carbon atoms in the alkyl or alkenyl radical, R1 is C1-C4alkyl and M1 is an alkali metal.
The non-ionic surfactant B) may be, for example, a condensation product of from 3 to 8 mols of ethylene oxide with 1 mol of primary alcohol that contains from 9 to 15 carbon atoms.
Suitable builder substances C) include, e.g., alkali metal phosphates, especially tripolyphosphates, carbonates or bicarbonates, especially the sodium salts thereof, silicates, aluminium silicates, polycarboxylates, polycarboxylic acids, organic phosphonates, aminoalkylenepoly(alkylenephosphonates) and mixtures of such compounds.
Silicates that are especially suitable are sodium salts of crystalline layer silicates of formula NaHSitO21+1.pH2O or Na2SitO21+1.pH2O, wherein t is a number from 1.9 to 4 and p is a number from 0 to 20.
Of the aluminium silicates, preference is given to those obtainable commercially under the names zeolite A, B, X and HS and to mixtures that comprise two or more of those components.
Of the polycarboxylates, preference is given to the polyhydroxycarboxylates, especially citrates, and acrylates and also copolymers thereof with maleic anhydride.
Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylenediamine disuccinate both in racemic form and the enantiomerically pure S,S-form.
Especially suitable phosphonates or aminoalkylenepoly(alkylenephosphonates) include alkali metal salts of 1-hydroxyethane-1,1-diphosphonic acid, nitrilo-tris(methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepenta-methylenephosphonic acid.
Suitable peroxide components D) include, for example, the organic and inorganic peroxides known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 10 to 95xc2x0 C.
The organic peroxides are, for example, mono- or poly-peroxides, especially organic peracids or salts thereof, such as phthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanedioic acid, diperoxynonanedioic acid, diperoxydecanedioic acid, diperoxyphthalic acid or salts thereof.
Preference is given, however, to the use of inorganic peroxides, such as, for example, persulfates, perborates, percarbonates and/or persilicates. It will be understood that it is also possible to use mixtures of inorganic and/or organic peroxides. The peroxides can be present in various crystalline forms and with various water contents, and they can also be used together with other inorganic or organic compounds for the purpose of improving their storage stability.
The addition of the peroxides to the washing agent is carried out preferably by mixing the components together, for example using a screw metering system and/or a fluidized bed mixer.
The washing agent may comprise, in addition to the combination according to the invention, one or more optical brighteners, for example from the group comprising bistriazinylamino-stilbenedisulfonic acid, bistdazolylstilbenedisulfonic acid, bisstyrylbiphenyl or bisbenzofuranylbiphenyl, a bisbenzoxalyl derivative, bisbenzimidazolyl derivative, coumarin derivative or a pyrazoline derivative.
The washing agents may furthermore comprise suspending agents for dirt, for example sodium carboxymethylcellulose, pH regulators, e.g. alkali metal or alkaline earth metal silicates, foam regulators, e.g. soap, salts for regulating the spray-drying and the granulating properties, e.g. sodium sulfate, perfumes and, optionally, antistatic agents and softeners, enzymes, such as amylase, bleaching agents, pigments and/or toning agents. It will be understood that such components must be stable with respect to the bleaching agent used.
Further preferred additives to the washing agents according to the invention are polymers that, when textile materials are being washed, inhibit staining caused by dyes in the washing liquor that have been released from the textile materials under the washing conditions. Such polymers are preferably polyvinylpyrrolidones which, as appropriate, may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range from 5000 to 60 000, more especially from 10 000 to 50 000. Such polymers are used preferably in an amount of from 0.05 to 5% by weight, especially from 0.2 to 1.7% by weight, based on the total weight of the washing agent.
In addition, the washing agents according to the invention may also comprise so-called perborate activators, such as, for example, TAED or TAGU. Preference is given to TAED, which is preferably used in an amount of from 0.05 to 5% by weight, especially from 0.2 to 1.7% by weight, based on the total weight of the washing agent.
Surprisingly, the manganese complexes of formula (1) also have a markedly improved bleach-catalyzing action on coloured stains on hard surfaces. The addition of such complexes in catalytic amounts to a dishwashing agent that comprises a peroxy compound and optionally TAED (N,N,Nxe2x80x2,Nxe2x80x2-tetraacetylethylenediamine) results in the substantial removal of tea stains from porcelain at 45xc2x0 C. in automatic dishwashers. This is the case even when hard water is used, it being known that tea deposits are more difficult to remove in hard water than in soft water.
The invention accordingly relates also to the use of manganese complexes of formula (1) as catalysts for reactions with peroxy compounds in cleaning solutions for hard surfaces, especially for crockery.
The invention relates furthermore to cleaning agents for hard surfaces, especially cleaning agents for crockery and, among such agents, preferably those for use in cleaning processes carried out by machine, which agents comprise one of the above-described compounds of formula (1) as bleach catalyst, and to a method of cleaning hard surfaces, especially crockery, using such a bleach catalyst.
The manganese complexes of formula (1) according to the invention are furthermore excellently suitable for cleaning hard surfaces, especially glazed tiles or floor tiles, especially for the removal of stains that have formed as a result of the action of molds (xe2x80x9cmold stainsxe2x80x9d). Such stains frequently occur in the joints between glazed tiles. The joints may consist, for example, of cement-containing and/or gypsum-containing material, or of polymers, for example silicone.
The invention accordingly relates also to the use of manganese complexes of formula (1) as catalysts for reactions with peroxy compounds in cleaning solutions for glazed tiles and floor tiles, or the joints between such tiles, and to the cleaning solutions used for that purpose comprising a manganese complex of formula (1) and a peroxide and optionally further additives, such as, for example, surfactants.
Used together with peroxy compounds, the manganese complexes of formula (1) according to the invention furthermore exhibit excellent antibacterial activity. The invention relates also to the use of the manganese complexes of formula (1) according to the invention to kill bacteria or to provide protection against attack by bacteria.
The following Examples serve to illustrate the invention without the invention being limited thereto. Parts and percentages relate to weight, unless specified otherwise. Preparation of the ligands is expediently carried out under an argon atmosphere.